Making sulphonated products



Patented June 4, 19 40 MAKING SULPHONATED PRODUCTS Bernard A. Dombrow, New York, N. Y and Ralph M. Beach, Newark, N. J., assignors toNational Oil Products Company, Harrison, N. J., a corporation of New Jersey No Drawing. Application March 2, 1937, Serial No. 128,600

18-Olaims. (Cl. 260 -400) The present invention is directed to novel sulphonated fatty oils and acids and is particularly directed to methods of producing the same. I

5 Although not restricted thereto, the present invention will be particularly described in its application to sulphonated acids and oils in which the acids consist of high molecular weight aliphatic carboxylic acids containing one or more hydroxy-groups and/or unsaturated bonds, and in which the oils consist of glycerides of these acids, as for example, olive oil or castor oil.

In the usual methods of producing sulphonated oils and acids of the character above described,

the oil or acid is treated with sulphuric acid or other sulphonating agents until a sulphonated acid or oil containing about 4 to 10% organically combined S0: is produced.

This sulphonated product is washed with water or salt solutions and also neutralized with alkalies.

It has been found that these finished sulphonated products are not stable, in that they tend to separate and also decompose in the presence of aqueous acid or salt solutions. This separation often results in the formation of undesirable sludge and in spotting or staining of fabrics where the sulphonated products are utilized in dyeing and finishing.

It is therefore among the objects of the present invention to provide an improved sulphonated product of the character above described which will be of enhanced stability, which will not tend to form a sludge or give rise to 'oily or fatty de- 5 posits upon standing or in the presence of acids or salts, and which can be most readily employed in the dyeing and finishing of textile fabrics without the above-mentioned disadvantages.

Another object is to provide an improved pro- 40 cedure for producing such desirable sulphonated products without the need of employing expensive equipment and reagents, with high yields and at low cost. g

It hasbeen found that sulphonated products of the character above described are greatly improved in their stability when the organically combined S03 content is increased to above 10%.

Suchproducts are also particularly resistant to formation of sludge or the separation of greasy 50 or fatty deposits upon standing or in the presence of acids or salts, particularly in dyeing and'finishing baths. These products of increased S03 content, however, are not readily produced by direct sulphonation. 55 In order to obtain high sulphonated products it has been proposed in some instances to oxidize and hydroxylate the aliphatic chains of the high molecular weight fatty acids and esters to provide more places for attachment of sulpho groups and thus enable the compounds to be 5 sulphonated to a higher degree, but these oxidation and hydroxylation methods do not produce high yields of the desired materials. In any case,

it is-not readily possible directly to increase the sulphonation of these fatty acids or oil products 10 to above 10% without extended and difiicult procedures involving substantial increased cost in raw materials and more expensive apparatus with decreased yields of the desired sulphonated product.

It is therefore among the further objects of the present invention to provide improved sulphonated oils and acids of increased S03 content at low cost and with maximum yields without the need of utilizing special sulphonation pro- 20 cedures or equipment.

Other objects will be obvious or will be apparent during the course of th\. following specification.

It appears that the usual sulphonated fatty oils or acids containing less than 10% of S03 contain substantial quantities of unsulphonated materials which .tend to give rise to the instability of the products. It further appears that when these unsulphonated materials are partly removed. to give a product of increased 503 content, the stability of the sulphonated material will be greatly enhanced.

In accomplishing the above objects according to the present invention it has now been found that these unsulphonated materials may be removed from the sulphonated products or that the sulphonated product may be most readily en. riched in respect to its S03 content by applying certain differential solvents to the finisher: sulphonated products.

These differential solvents are preferably of such a nature as to dissolve the unsulphonated component in preference to the sulphonated components of the sulphonated product, although solvents having a preference for the sulphonated may be used in certain instances. Among the differential solvents which may be employed are halogenated and readily volatilized aliphatic and aromatic hydrocarbons and their derivatives, of

the type adapted to dissolve out unsulphonated fatty material in the presence of sulphonated fatty material without the addition of water.

Among the preferred materials which may be employed are the alkylene dichlorides containing from 2 to 5 carbon atoms, ethylene dichloride and propylene dichloride being preferred. These alkylene dichlorides are particularly suitable as differential solvents to be employed with the sulphonated fatty acids and fatty oils.

These solvents are generally most desirably employed at room temperatures or at somewhat lower temperatures. Other chlorinated solvents such as chloroform, orthodichlorbenzene, dichlorethylether, trichlorbutane and so forth may also be employed.

Generally speaking, non-halogenated aliphatic or aromatic hydrocarbons and their nonhalogenated derivatives are not suitable under the conditions set forth, and chlorinated aliphatic or aromatic hydrocarbons and their chlorinated derivatives are preferred.

In applying these differential solvents which may be utilized in mixtures, but which are preferably utilized singly, the sulphonated oil or acid is treated with the same or a substantially greater volume or weight of the solvent, the preferred ratioof solvent to the sulphonated product being 1 to 4 volumes of the former to one volume of the latter.

After thorough agitation and mixture the combination is permitted to settle and there will be a separationv in two layers, one layer containing the sulphonated product of increased SO: concentration and the other layer containing most of the solvent together with a substantial amount of the unsulphonated products.

This extraction may be repeated several times and it may take place at temperatures varying from room temperature to 0 C. or lower.

The upper layer which contains the sulphonated products of increased SO: concentration then may be heated to volatilize and to distill away difierential solvent included therein with the result that there is obtained a sulphonated oil or acid of increased S03 content varying from 10% to 16% or higher.

The other layer may be treated to remove and recover the volatile solvent and the residue may then be utilized as raw material for further sulphonation procedures.

Example I I 1,000 gm. of sulphonated olive oil having an S0; content of 8.56% were extracted 3 times at 10 0., 2,000 gm. of propylene dichloride being utilized for each extraction. After each extraction thelower layer containing 'most of the solvent and the extracted unsulphonated materials were separated and the final upper layer, after removal of the solvent taken up therein,

gave 545 gm. of a sulphonated olive oil having an S0: content of 11.1%.

Approximately of the S03 originally present was therefore recovered in the. final sulphonated product. I

Example II 500 gm. of sulphonated olive oil having an S0: content of 8.12% were extracted twice with dichlorethylether at 0 C. 'I'he final upper layer containing the sulphonatedproduct of increased SO: content was then separated from the lower content of 11.2%.

layer containing a large proportion of the unsulphonated material. Removal of the residual solvent from the separated upper layer yielded 245 gm. of a sulphonated olive Example III 1,000 gm. oi sulphonated oleic'acid having an SOa'COntBht of 8.87% were extracted once with 3 'volumes of ethylene dichloride. The yield was 623 gm. of a sulphonated 'oleic acid having an S0: content of- 13.35%, a recovery of approximately 94% of the original S03.

Example IV I 1.000 gin. of sulphonated oleic acid having an S03 content of 9.37% were extracted twice with 2,000 cc. of ethylene dichloride at room temperature. After removal of the residual solvent from the sulphonated product, the yield was .565 gm. of a sulphonated oleic acid of 15.84% SO: content.

Examplell well mixed with the sulphonated product and after thorough agitation the mixture was allowed to separate, the temperature being lowered if necessary to obtain better separation. If desired, the separation can also be speeded by use of the centrifuge.

While the amount of solvent used for each extraction may be varied, it has ben found that from about 1 to 4 volumes of solvent, as against 1 volume of sulphonated product, give the best rate of separation and the most eflicientconcentration of S0: in the upper layer with the minimum number of extractions. Y

oil having an Smaller or larger ratios of solvent to sul-- phonated product" can be used, but too small a volume of solvent may entirely dissolve into the sulphonated product while too large a volume may not give eflicient separation.

The volume of solvent used and number :of

extractions made depend entirely on the amount of combined S0: desired in the final product.

When the product is to be used in nearly neutral or only mildly acid media, it has been found that a percentage of combined SO: be-

tween 10 and 13% will be satisfactoryfwhile the higher acidity provided by 1% or more of HCl,. for example, would make more desirable a prod* not having a combined 80; content of more than 13%, if it is to be stable in such a medium.

The products producedare not only of increased S03 content as above mentioned, but are of enhanced stability, particularly in regard to media containing substantial quantities of acids or salts. And this enhanced stability is more than would be expected from'the increase in S0: content. The material also has particularly de-. sirable characteristics due to the decrease in the. amount of unsulphonated materials ,therein and number of industrial applications and the following examples of such applications are not in tended to be limiting, but are'given merely to illustrate some of the many uses of these 5 products.

Example VI Example VII In the finishing of fabrics, the high 503 content products of Examples I to V may be usedin the presence of even large amounts of gums and salts such as sulphates, e. g., magnesium sulphate, without the salting out of fatty or greasy deposits as, occurs with ordinary sulphonated products.

Example VIII The products of Examples I'to V are valuable as wetting agents Powdered sulphur, for example, is successfully made wettable by the incorporation of as little as 1% of high S03 sulphonated fatty acids or fatty acid derivatives above described. In addition, the resultant dispersions of sulphur or similar products remain stable in the presence of hydrochloric acid or other acids often used in connection with insecticidal sprays, fruit washing and spraying solutions, and so forth. Similarly satisfactory results cannot be obtained with ordinary sulphonated oils or soaps.

Although in the preferred procedures emphasized above, olive oil and oleic acid are specifically described as materials to be sulphonated and afterwards to be subjected to the separation process, it is also possible to utilize the present process in connection with sulphonated castor oil, corn oil, fish oils, sperm oil, neatsfoot oil, linseed oil, lard oil, rapeseed oil,

soya bean oil, cocoanut oil, cottonseed oil and so forth and their corresponding fatty acids. Esters otherthan the glycerides may also be processed.

Less preferably the concentration process of the present application may also be applied to other sulphonated unsaturated aliphatic compounds and to sulphonated saturated aliphatic compounds or to sulphonated combinations containing higher fatty alcohols, aldehydes and ketones, such as, for example those containing 8 to 24 carbon atoms.

If desired, the extraction or separation process of the present invention may be applied to sulphonated products containing other percentages of S03 than the 4 to 10 percent mentioned as obtained in ordinary sulphonation.

It may also be desirable, in connection with certain processes and with certain oils or fatty acids, to incorporate the solvent in part or whole with the oil or acid or other fatty material before the sulphonation. The solvent may be left in the mixture during the subsequent neutralization or washing operations and finally the separation may be caused to take place with It will not break and dispersing agents.

or without the addition of differential solvent as necessary.

By the term differential solvent as used in the accompanying specification and claims is included liquid organic solvents capable of concentrating thesulphonated components of the sulphonated product by removing the unsulphonated components by reason of a preferential solvent power for such unsulphonated components. Preferably the solvent should be of such nature as to form a layer containing unsulphonated components which is readily separated from another layer containing the concentrated sulphonated products. Sometimes the differential solvent may have] a preferential solvent action on the sulphonated components, instead of the unsulphonated components.

In addition the concentration of the sulphonated product by means of the differential solvent may be obtained in other manners than by causing layer-formation and separating the layers. The expression fsulphonated when used in conjunction with fatty acids, glycerides, etc. is'employed herein to designate the neutralized sulphonation products of the respective fatty acids, glycerides, etc.

Many other changes could be effected in the particular features of the process disclosed and in specific details thereof, without substantially departing from the invention intended to be defined in the claims, the specific description herein merely serving to illustrate certain elements by which, in one embodiment, the spirit of the invention may be effectuated.

What we claim is: H

1. In a process for increasing the S03 content of sulphonated fatty acids, fatty glycerides and fatty derivatives, the step which consists in sub-. jecting the sulphonated material to extraction with a fluid consisting of a halogenated organic solvent which fluid is a solvent for unsulphonated.

fatty material in the presence of sulphonated fatty material.

2. A process for increasing the S03 content of sulphonated fatty acids, fatty glycerides and fatty derivatives, which comprises mixing such sulphonated materials with a non-aqueous liquid consisting of at least one halogenated organicsolvent which liquid is a solvent for unsu1-' phonated fatty material in the presence of sulphonated fatty material, allowing the mixture to settle whereby two layers form, one containing sulphonated fatty material'and the other containing dissolved unsulphonated fatty material and separating the respective layers of material. 3. The process in accordance with claim 1 wherein the solvent used 'is a low molecular weight alkylene dichloride.

4. The process in accordance with claim 1 wherein the solvent used is ethylene dichloride.

5. The process in accordance with claim 1 wherein the solvent used is dichlorocthylether.

6. The process in accordance with claim 1 wherein the solvent used is orthodichlorobenzol.

'7. In a process for increasing the S03 content of sulphonated oleic acid, the step which consists in subjecting sulphonated oleic acid to extraction with a non-aqueous liquid consisting of a halogenated organic solvent which liquid is a solvent for unsulphonated oleic acid in the presence of sulphonated oleic acid.

8. In a process for increasing the E303 content of sulphonated olive oil, the step whibh consists in subjectingsulphonated olive oil toiextraction with a non-aqueous liquid consisting'of a halobetween 8% and 9% which comprises mixing and genated organic solvent which liquid a solvent for unsulphonated olive oil in the presence of sulphonated olive oil.

9. In a process for increasing the S03 content.

of sulphonated oleic acid, the step which comprises subjecting the sulphonated oleic acid to extraction with a liquid solvent consisting of ethylene dichloride. i

10. In a process for increasing the S03 content of sulphonated olive oil, the step which comprises subjecting the sulphonated olive oil to extraction with a liquid solvent consisting of dichloroethylether.

' 11. A process of increasing the SO: content of sulphonated olive oil having an S0: content of agitating the sulphonated oil several times with a low molecular weight liquid alkylene dichloride at about between 0 C. to 10 C., separating the lower layer containing most of the dichloride and the extracted unsulphonated materials and treating the upper layer to remove the dichloride and recover the sulphonated oil of increased. SO;

content.

, 12. A process of increasing the S03 content of sulphonated olive oil having an S0: content of between 8% and 9% which comprising mixing and agitating the sulphonated oil several times with a low molecular weight liquid dichloralkyl ether at about between 0 C. to 10 0., separating the lower layer containing most of the ether and the extracted unsulphonated materials and treating the upper layer to remove the ether and recover the sulphonated oil of increased S01 content.

13. The process of claim 11 in which the,

dichloride is ethylene dichloride.

14. The process of claim 12 in which the ether is dichlorethyl ether. 15. The process of claim. 11 in which the dichloride is used in greater volume than the sulphonated oil in each extraction.

16. A process of increasing the S03 content of sulphonated oleic acid having an S0: content of between 8% and 10% which comprises mixing and agitating the sulphonated oleic acid with several volumes of an alkylene dichloride at about between. 0 C. and room temperature separating the lower layer containing most of the dichloride and the extracted unsulphonated' oleic acid, and

treating the upper layer to remove the dichloride 

